Electronic Supporting Information Facile “one pot” route ... · Electronic Supporting Information Facile “one pot” route to the novel benzazulene–type dye class: asymmetric,

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Electronic Supporting Information

Facile “one pot” route to the novel benzazulene–type dye class:

asymmetric, derivatizable, 5–7–6 fused ring puckered half BODIPY

design

Dhiraj P. Murale, Kang Mun Lee, Kibong Kim and David G. Churchill*,a

Molecular Logic Gate Laboratory, Department of Chemistry, Department of Chemistry, Korea

Advanced Institute of Science and Technology (KAIST), 373–1 Guseong–dong, Yuseong–gu,

Daejeon, 305–701, Republic of Korea. Fax: (+82)42–350–2810; Tel: (+82)42–350–2845;

E–mail: [email protected]

Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011

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Experimental Section

General Remarks. All reagents used herein were used as received from the suppliers

(Aldrich, Acros, and Junsei companies). Melting points were taken on an electro–thermal

melting point apparatus and are reported uncorrected. Synthetic details for the preparation of the

dipyrromethanes and for the BODIPY systems follow literature methods. 1H and 13C NMR

spectra were acquired using a Bruker Avance 400 MHz spectrometer. TMS was used as an

internal standard. 1H and 13C NMR spectral signals were calibrated internally by the respective

protio impurity or carbon resonance of the NMR spectroscopic solvent e.g., CDCl3 (1H: δ 7.24;

13C: δ 77.0). High resolution matrix–assisted laser desorption/ionization (MALDI) mass

spectrometry was performed on a VG AUTOSPEC ULTIMA by the research support staff at

KAIST. This instrument possesses a trisector double focusing magnetic sector analyzer and was

operated at a resolution of 80,000. Absorption spectra were measured using a JASCO V–530

UV/Vis spectrophotometer. Fluorescence measurements were carried out with a Shimadzu RF–

5301pc spectrofluorophotometer.


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Experimental procedure for compound (1):

In a round bottom flask, 2–methylaminobenzaldehyde (300 mg, 2.20 mmol) was taken in

dichloromethane at 0 ºC under argon and treated with 2,4–dimethylpyrrole (0.42 mL, 4.4 mmol)

and 2 drops of trifluoroacetic acid and allowed to stir for ~1.0 h, followed by addition of 2,3–

dichloro–5,6–dicyanobenzoquinone( DDQ) (499 mg, 2.20 mmol). At the same temperature after

additional stirring for ~1.0 h, triethylamine (3.0 mL, 0.022 mol) was added, followed by

BF3·OEt2 (2.7 mL, 0.022 mol); stirring continued overnight. The reaction mixture was passed

through a silica pad, followed by PTLC purification of the residue after rotary evaporation of the

filtrate to give required BODIPY as red solid (80 mg, 10.2 %).

NH

O

Me1. 2,4-dimethylpyrrole2. DDQ3. Et3N, BF3·OEt2

Dichloromethane, argon. 0ºC

NB

N

Me

Me

Me

Me

1

NH

Me

FF

Scheme 1: synthesis of compound 1.


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Experimental procedure for synthesis of novel compound 2 (and analogues):

A round bottom flask evacuated with argon, was charged with 4–

diethylaminosalicylaldehyde (500 mg, 2.58 mmol), followed by the addition of 2,4–

dimethylpyrrole (0.50 mL, 5.17mmol) and 2 drops of trifluoroacetic acid in dichloromethane (ca.

30 mL) at 0 ºC. This mixture was allowed to stir for ~1.0 h. To the reaction mixture, with the

temperature maintained at 0 ºC, 2,3–dichloro–5,6–dicyanobenzoquinone (DDQ) (587 mg, 2.58

mmol) was added; the reaction mixture was stirred for another ~1.0 h. Lastly, at the same

temperature, triethylamine (3.6 mL, 0.0258 mol) was added and BF3·OEt2 (3.2 mL, 0.0258 mol);

the reaction mixture was allowed to stir overnight. Ultimately, the reaction mixture was passed

through a silica pad and the residue further purified by PTLC after rotary evaporation to obtain

the required compound as a (yellow fluorescent) red solid (350 mg, 43%). [Note: Analogous

syntheses were made for compounds deriving from these salicylaldehyde starting materials: 5–

methoxysalicylaldehyde, 5–bromosalicylaldehyde, 4–methoxysalicylaldehyde, and 2–hydroxy–

1–naphthaldehyde.]

N

BO

F F

NOH

N

O

1. 2,4-dimethylpyrrole2. DDQ3. Et3N, BF3·OEt2

Dichloromethane, argon. 0ºC

2

1

23

45

6

7

8

a

b

c

d

e

f

Scheme 2: Synthesis of compound 2.


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Experimental procedure for synthesis of compounds (2 a–b):

In a round bottom flask, compound 2 (100 mg, 0.314 mmol) was taken in benzene (ca. 30

mL); this mixture was treated with 2–thiophenecarboxaldehyde (0.05 mL, 0.062 mmol), glacial

acetic acid (0.5 mL) and piperidine (0.5 mL). The reaction mixture was refluxed to dryness.

Water was added and organic layer was separated and washed with water (2 times). The organic

solvent was isolated, reduced in volume by rotary evaporation, and purified by column

chromatography, followed by PTLC purification as well to give the product as a blue solid (27

mg, 20.8 %).

Acetic acid, Piperidine,Benzene, reflux.

Ar-CHO

N

BO

F F

N

N

BO

F F

NAr

Scheme 3: Synthesis of compound 2a – b.


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Fig. S1: 1H NMR spectrum of compound 1.


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Fig. S2: 13C NMR spectrum of compound 1.


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Fig. S3: ESI MASS spectrum of compound 1.


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Fig. S4 :11B NMR spectrum of compound 1.


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Fig. S5: 19F NMR spectrum of compound 1.


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Fig. S6: 1H–1H COSY NMR spectrum of compound 1.


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Fig. S7: 1H–1H NOESY NMR spectrum of compound 1.


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Fig. S8: 1H–1H HSQC NMR spectrum of compound 1.


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Fig. S9: 1H–coupled NMR spectrum of compound.


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1

Fig. S10: 1H–1H HMBC NMR spectrum of compound 1.


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Fig. S11: 1H NMR spectrum of compound 2.

N

B

O

N

F

F


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Fig.S12: 13C NMR spectrum of compound 2.

N

B

O

N

F

F


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Fig.S13: 11B NMR spectrum of compound 2.

N

B

O

N

F

F


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Fig.S14: 19F NMR spectrum of compound 2.

N

B

O

N

F

F


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Fig S15: 1H–13C HSQC NMR spectrum of compound 2.


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Fig. S16: 1H–13C HMBC NMR spectrum of compound 2.


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Fig S17: 1H–1H COSY NMR spectrum of compound 2.


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Fig. S18: ESI mass spectrum of compound 2.


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Fig. S19: 1H NMR spectrum of compound 2a.


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Fig. S20: 13C NMR spectrum of compound 2a.


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Fig. S21: ESI mass spectrum of compound 2a.


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Fig. S22: 1H NMR spectrum of compound 2b.


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Fig. S23: 13C NMR spectrum of compound 2b.


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Fig. S24: ESI mass spectrum for compound 2b.


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Fig. S25: 1H NMR spectrum of pure “half–BODIPY” product from reaction of 2,4–dimethylpyrrole and 4–methoxysalicylaldehyde.


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Fig. S26: 13C NMR spectrum of pure “half– BODIPY” product from the reaction of 2,4–dimethylpyrrole and 4–methoxysalicylaldehyde.


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Fig. S27: 11B NMR spectrum of pure “half– BODIPY” product from the reaction of 2,4–dimethylpyrrole and 4–methoxysalicylaldehyde.


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Fig. S28: ESI mass spectrum of pure “half–BODIPY” product from the reaction of 2,4–dimethylpyrrole and 4–methoxysalicylaldehyde.


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Fig. S29: 1H NMR spectrum of pure “half–BODIPY” product from the reaction of 2,4–dimethylpyrrole with 2–hydroxy–1–naphthaldehyde.


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Fig. S30: 13C NMR spectrum of pure “half–BODIPY” product from the reaction of 2,4–dimethylpyrrole with 2–hydroxy–1–naphthaldehyde.


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Fig. S31: 11B NMR spectrum of pure “half–BODIPY” product from reaction of 2,4–

dimethylpyrrole and 2–hydroxy–1–naphthaldehyde.


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Fig. S32: ESI mass spectrum of pure “half–BODIPY” product from the reaction of 2,4–dimethylpyrrole with 2–hydroxy–1–naphthaldehyde.


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Fig. S33: 1H NMR spectrum of pure “half–BODIPY” product from reaction of 2,4–dimethylpyrrole with 5–methoxysalicylaldehyde.


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Fig. S34: ESI mass spectrum of pure “half–BODIPY” product from reaction of 2,4–dimethylpyrrole with 5–methoxysalicylaldehyde.


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Fig. S35: 1H NMR spectrum of pure “half–BODIPY” product from reaction of 2,4–dimethylpyrrole and 5–bromosalicylaldehyde.


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Fig. S36: ESI mass spectrum of pure “half–BODIPY” product from the reaction of 2,4–dimethylpyrrole and 5–bromosalicylaldehyde.


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Spectroscopic Data for “half– BODIPY” product from reaction of 2,4–

dimethylpyrrole with 2–hydroxynaphthaldehyde: 1H NMR (400 MHz, CDCl3, δ 7.24): δ =

8.18 (s, 1H), 8.08 (d, 1H, 3JH–H = 8.5 Hz), 7.98 (d, 1H, 3JH–H = 8.9 Hz), 7.80 (d, 1H, 3JH–H = 8.0

Hz), 7.60 (t, 1H, 3JH–H = 7.0 Hz), 7.44 (t, 1H, 3JH–H = 7.1 Hz), 7.32 (d, 1H, 3JH–H = 8.9 Hz), 6.42

(s, 1H), 2.68 (s, 3H), 2.46 (s, 3H). 13C–NMR (100 MHz, CDCl3, δ = 77.0): δ =167.6, 161.5,

150.2, 141.7, 138.7, 133.9, 130.0, 129.4, 128.6, 125.1, 124.8, 124.0, 121.7, 116.5, 16.5, 12.3.

11B–NMR (CDCl3, BF3·OEt2, δ 0.00): δ 1.06 (t, 1JB–F= 18.8 Hz). MS: Calculated for

C17H14BF2NO, M = 297.10; found M = 320.10 (M + Na+).


dimethylpyrrole with 4–methoxysalicylaldehyde:4–METHOXY: 1H NMR (400 MHz, CDCl3,

δ 7.24): δ = 7.29 (d, 1H, 3JH–H = 8.7 Hz), 7.24 (s, 1H), 6.68 (s, 1H), 6.59 (d, 1H, 3JH–H = 8.7 Hz),

6.35 (s, 1H), 3.86 (s, 3H), 2.63 (s, 3H), 2.34 (s, 3H). 13C–NMR (100 MHz, CDCl3, δ = 77.0): δ

=167.6, 167.0, 162.2, 149.8, 139.9, 138.0, 136.1, 124.7, 117.1, 111.1, 106.0, 55.8, 30.9, 16.5,

12.1. 11B–NMR (CDCl3, BF3·OEt2, δ 0.00): δ 0.91 (t, 1JB–F= 19.7 Hz). MS: Calculated for

C14H14BF2NO2, M = 277.07; found M = 300.10 (M + Na+).


dimethylpyrrole with 5–methoxysalicylaldehyde:5–METHOXY: 1H NMR (300 MHz, CDCl3,

δ 7.24): δ = 7.23 (s, 1H), 7.13 (s, 1H), 7.12 (s, 1H), 6.80 (s, 1H), 6.42 (s, 1H), 3.79 (s, 3H), 2.68


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(s, 3H), 2.38 (s, 3H). MS: Calculated for C14H14BF2NO2, M = 277.07; found M = 300.10 (M +

Na+).


dimethylpyrrole with 5–bromosalicylaldehyde:5–BROMO: 1H NMR (400 MHz, CDCl3, δ

7.24): δ = 7.53 (m, 2H), 7.16 (s, 1H), 7.07 (d, 1H, 3JH–H = 8.5 Hz), 6.45 (s, 1H), 2.69 (s, 3H),

2.37 (s, 3H). MS: Calculated for C13H11BBrF2NO, M = 325.94; found M = 350.00 (M + Na++

H+)


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Table 1. Crystal data and structure refinement for 1 (CCDC # 831215). Identification code 1 Empirical formula C20 H22 B F2 N3 Formula weight 353.22 Temperature 296(2) K Wavelength 0.71073 Å Crystal system Orthorhombic Space group Pbca Unit cell dimensions a = 12.7459(15) Å = 90°.　 b = 12.7700(13) Å = 90°.　 c = 23.352(3) Å = 90°.　 Volume 3800.9(7) Å3 Z 8 Density (calculated) 1.235 Mg/m3 Absorption coefficient 0.087 mm–1 F(000) 1488 Crystal size 0.3 x 0.15 x 0.1 mm Theta range for data collection 1.74 to 24.80°. Index ranges –14<=h<=14, –14<=k<=15, –27<=l<=27 Reflections collected 22184 Independent reflections 3254 [R(int) = 0.1506] Completeness to theta = 24.80° 99.4 % Refinement method Full–matrix least–squares on F2 Data / restraints / parameters 3254 / 0 / 245 Goodness–of–fit on F2 1.014 Final R indices [I>2 sigma(I)] R1 = 0.0643, wR2 = 0.1337 R indices (all data) R1 = 0.1527, wR2 = 0.1860 Extinction coefficient 0.0193(17) Largest diff. peak and hole 0.461 and –0.420 e/Å–3


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Table 2. Crystal data structure refinement for 2 (CCDC # 822264). Identification code 2 Empirical formula C17H21BF2N2O Formula weight 318.17 Temperature 296(2) K Wavelength 0.71073 Å Crystal system Monoclinic Space group P2(1)/c Unit cell dimensions a = 9.0254(19) Å = 90°.　 b = 11.308(2) Å = 93.845(6)°.　 c = 16.035(4) Å = 90°.　 Volume 1632.9(6) Å3 Z 4 Density (calculated) 1.294 Mg/m3 Absorption coefficient 0.096 mm–1 F(000) 672 Crystal size 0.4 x 0.3 x 0.2 mm Theta range for data collection 2.21 to 24.30°. Index ranges –10<=h<=10, –13<=k<=13, –18<=l<=18 Reflections collected 17948 Independent reflections 2652 [R(int) = 0.0423] Completeness to theta = 24.30° 99.6 % Refinement method Full–matrix least–squares on F2 Data / restraints / parameters 2652 / 0 / 212 Goodness–of–fit on F2 1.029 Final R indices [I>2sigma(I)] R1 = 0.0608, wR2 = 0.1632 R indices (all data) R1 = 0.0815, wR2 = 0.1790 Extinction coefficient 0.000(2) Largest diff. peak and hole 0.688 and –0.213 e/Å–3


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Table 3. Crystal data and structure refinement for 2a (CCDC # 830331). Identification code 2a Empirical formula C22 H23 BF2 N2OS Formula weight 412.29 Temperature 296(2) K Wavelength 0.71073 Å Crystal system Monoclinic Space group C2/c

Unit cell dimensions a = 20.366(9) Å = 90°.　 b = 7.556(3) Å = 106.43(3)°.　 c = 27.882(12) Å = 90°.　 Volume 4115(3) Å3 Z 8 Density (calculated) 1.331 Mg/m3 Absorption coefficient 0.191 mm–1 F(000) 1728 Crystal size 0.25 x 0.22 x 0.12 mm3 Theta range for data collection 2.09 to 28.36°. Index ranges –21<=h<=27, –10<=k<=9, –35<=l<=37 Reflections collected 15529 Independent reflections 5067 [R(int) = 0.1113] Completeness to theta = 28.36° 98.4 % Max. and min. transmission 0.9775 and 0.9539 Refinement method Full–matrix least–squares on F2 Data / restraints / parameters 5067 / 0 / 265 Goodness–of–fit on F2 1.016 Final R indices [I>2sigma(I)] R1 = 0.0802, wR2 = 0.1734 R indices (all data) R1 = 0.2109, wR2 = 0.2139 Extinction coefficient 0.0046(7) Largest diff. peak and hole 0.332 and –0.446 e/Å–3


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400 500 600 700

0.0

0.1

0.2

0.3

0.4 absorbance emission

Wavelength (nm)

Abs

orba

nce

-100

0

100

200

300

400

500

600

700

800

Em

ission intensity

Fig. S37: Absoption and emission spectrum of compound 2 in acetonitrile.


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350 400 450 500 550 600 650 700

0.0

0.2

0.4

0.6

0.8

1.0

Abso

rban

ce

Wavelength (nm)

Normalised 2a Normalised 2b

Fig. S38: Absorption spectrum of compound 2a and 2b in acetonitrile.

500 550 600 650 7000

50

100

150

200

250

300

350

Emis

sion

inte

nsity

Wavelength (nm)

2b 2a

Fig. S39: Emission spectrum of compound 2a and 2b in acetonitrile.


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Fig. S40: Comparison of different anions with fluoride anion for compound 1

( 5 × 10 –5 ).


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Fig. S 41: pH titration data for compound 1 against buffer solutions at different pH’s.


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Fig S42: Appearance of compounds 1, 2, 2a, 2b (from left to right) under white light.

Fig S43: Appearance of compounds 1, 2, 2a, 2b (from left to right) under UV lamp (365nm).

-- END --


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Electronic Supporting Information Facile “one pot” route ... · Electronic Supporting Information Facile “one pot” route to the novel benzazulene–type dye class: asymmetric,